Tris(1-aziridinyl)phosphazo hardeners



United States Patent O 3,549,378 TRIS(1-AZIRIDINYL)PHOSPHAZO HARDENERS Donald M. Burness and Robert A. Silverman, Rochester,

N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey N Drawing. Continuation-impart of abandoned application Ser. No. 475,599, July 28, 1965. This application Feb. 5, 1969, Ser. No. 796,929

Int. Cl. G03c 1/30 US. Cl. 96111 30 Claims ABSTRACT OF THE DISCLOSURE are illustrative of the aziridine hardener compounds employed.

This application is a continuation-in-part of our copending application Ser. No. 475,599 filed July 28, 1965.

This invention relates to hydrophilic compositions hardened with a hardening amount of the aziridine hardener compounds defined hereinafter. It relates, for example, to gelatin compositions including gelatin-silver halide emulsions containing therein as a hardener a substituted aziridine derived from a carboxamide, a sulfonamide or a phosphamide by treating the amide with phosphorus pentachloride followed by reaction with ethylenimine.

The hardening action of aziridines is well known in the art. Various bisaziridines and trisaziridines have been suggested as hardeners for gelatin. These compounds have on the whole shown themselves to be good gelatin hardeners except for considerable toxicity. Other aziridine compounds with somewhat less toxicity have been suggested as hardeners for gelatin.

One object of our invention is to provide gelatin hardeners which do not fog or desensitize gelatino silver halide photographic emulsions. Another object of our invention is to provide aziridine type hardeners considerably less toxic than many hardeners of this type suggested in the art. A further object of our invention is to provide hardeners that are useful for hardening hydrophilic materials such as gelatin, casein and carboxylated polymers, for example. A still further object of our invention is to provide gelatin hardeners that will Withstand high temperature processing techniques as are often desirable for speeding up processing of photographic emulsions. Other objects of our invention will appear herein.

The carboxylated polymers mentioned herein may be polymers or copolymers prepared in part from acrylic acid or maleic anhydride or they may be derived polymers containing pendant carboxyl groups. Examples of the latter would be products prepared by reaction of maleic or phthalic anhydrides on polyvinyl alcohol or cellulose derivatives. The carboxylated polymers mentioned herein include copolymers derived from maleic anhydride and vinyl acetate as well as copolymers derived from acrylic acid and ethyl acrylate, for example.

3,549,378 Patented Dec. 22, 1970 "ice The hardeners in accordance with our invention for the most part are made by reacting monoor diamide compounds such as carboxamides, sulfonamides, phosphamides or the like with phosphorus pentachloride followed by reaction with ethylenimine. The compounds prepared using diamides as the starting material ordinarily result in hexa-aziridine derivatives which are excellent hardeners for gelatin including gelatin-silver halide emulsions and for carboxyl polymers. The following illustrates the course of the reaction in preparing an aziridine derivative from a diamide:

t ad] When a Monoamide is used as the starting material, a three aziridine group containing compound is ordinarily obtained and these compounds are also useful as hardeners for gelatin and for carboxylated polymers. That reaction is illustrated by the following:

attached to a carbonyl, sulfonyl or phosphoryl linkage which in turn is attached to another organic radical. These are mostly represented by the following formula:

in which R is or a mono, bi or tervalent alkyl, aryl, aralkyl, cycloalkyl or heterocyclic radical and/or a substituted derivative thereof; R is H, CH or C H X is CO, S0 P0 or a combination thereof, m is 1 or 2, and n is l, 2 or 3. Compounds useful as hardeners in accordance with our invention are as follows:

derived from the Diels Alder adducts of maleic anhydride The following examples illustrate our invention but it is to be understood that these examples are not limiting.

EXAMPLE 1 An aziridine derivative was prepared by reacting sulfamide with phosphorus pentachloride and ethylenimine by the procedure described by Kirsanov et al., J. Gen. Chem. (U.S.S.R.) (English transl.) 31, 3200 (1961). The colorless solid, bis-[tri(1-aziridi11yl)phosphazo] sulfone, had a melting point of 93.5-94.5. This compound was used as a hardener in a gelatin-silver halide emulsion by adding portions thereof to separate portions of a high speed silver bromoiodide emulsion. Each emulsion sample was coated on a cellulose acetate film support at a coverage of 459 mg. of silver and 1040 mg. of gelatin per square foot. A sample of each film coating was exposed on an Eastman 1B sensitometer, processed for five minutes in Kodak DK- developer, fixed, washed, and dried with the following results:

Fresh Percent Concentration, Rel. swell in g./mole Ag speed Gamma Fog water EXAMPLE 2 TABLE I Analysis Calculated Found R R X n M.P. C. C H N 01 C H N Cl Hardener:

A C1 0 H CO 1 62-63 30.3 3.8 33.4 30.5 3.7 33.6 B C 11 H CO 1 54.5-55.5 56.5 6.2 20.2 56.2 6.2 19.9 C. CqH5 H S02 1 98.5-99 46.2 5.5 17.9 45.8 5.3 17.6 D pC H H 00 2 176 (100. 50.5 5.9 23 6 50.4 6.2 23.4

F N=P(N CH3 S02 1 44.2 7.4 22.8 43.0 7.9 20.2

G- OH; H S02 1 116-117 33.5 6.0 22.4 33.6 6.1 22.3 H iii-C 11 H CO 2 143.5-144 50.5 5.9 23.6 50.5 6.2 23.3

with dienes such as butadiene, cyclopentadiene or the like exemplified by CONHz CONH2 and CONH2 C0NI-I respectively.

Kodak DK5O developer, fixed, washed, and dried. Tests were run on the fresh samples. The results obtained with the various samples were as follows:

aldehyde-type gelatin hardeners with substituted aziridine hardeners of the type described herein.

, TABLE II Fresh 1 week incubation 2 weeks incubation verticnll swe l Cone. Rel. Rel. Rel. in H2O Hardener (g./m.) speed Gamma Fog speed Gamma Fog speed Gamma Fog (percent) None 100 1. 24 14 71. 1. 09 17 49.00 .91 .34 720 7. 2 94 1. 18 10. 20 65 .50 3. .45 83 380 14.4 97 1. 17 14 2. 38 280 100 1. 29 14 85. 00 1. 07 720 2. 4 89 1. 32 12 19. 00 470 7. 2 89 1. 25 11 1 370 14.4 89 1. 22 10 1 360 100 1. 25 11 85. 00 1. 06 730 2. 4 100 1. 27 1O 14. 00 75 340 7. 2 95 1. 23 10 7. 10 52 250 14. 4 95 1. 22 10 2. 90 .40 190 2. 4 97 1. 28 10 1 440 7. 2 97 1. 22 11 1. 290 14.4 97 1. 17 09 1. .37 250 100 1. 28 11 87. 00 1. 15 770 2. 4 91 1. 33 .09 19. 50 .83 480 7. 2 1. 47 10 5. 50 .57 310 14.4 82 1. 20 12 2. 05 42 260 2. 4 94 l. 32 10 6. 70 53 420 7. 2 1. 23 10 2. 20 .38 290 14.4 97 1. l8 10 0.91 32 230 2. 4 107 1. 32 10 17. 50 83 380 7. 2 1. 22 09 9. 50 57 240 14. 4 105 1. 13 l0 3. 80 38 200 EXAMPLE 3 A series of coatlngs where la1d down upon a paper Percent I-Iardener Rel. swell in (g./Ag mole) speed Gamma Fog water The substituted aziridine hardeners described herein are of value for gelatin compositions containing couplers. Photographic color print materials ordinarily include gelatin layers containing silver halide and a coupler corresponding to the type of sensitivity of the photographic emulsion. It is desirable to include in these layers some kind of a gelatin hardener to render those layers resistant to disintegration by aqueous processing solutions. The commonly used gelatin hardeners do not prevent and oftentimes promote staining of paper or other supports upon which these layers reside which may adversely affect the quality of the prints obtained therefrom.

The hardeners listed herein are of value in gelatin compositions containing couplers as applied to a support such as of paper whereby staining is minimized or even inhibited when those products are used for making photographic prints. Our invention is useful for instance in emulsions containing pyrazolone couplers such as those described in US. Pat. No. 2,600,799 of Loria et al. We have found that gelatin compositions containing couplers and hardeners, the hardener being of the type described herein, have good brightness characteristics and are more free of stain than compositions of like nature in which hardeners of some other types are used. The following example illustrates the advantage of our invention in the obtaining of photographic prints from materials used in accordance with our invention:

EXAMPLE 4 This example illustrates color photographic print materials comparing the results obtained using conventional support as follows:

Layer 6.-a gelatin layer.

Layer 5.a red-sensitive gelatino silver chlorobromide emulsion, of which approximately 90 mole percent of the halide is bromide containing a phenolic cyan coupler of the type described in US. Pat. 2,423,730.

Layer 4.--a gelatin layer containing an ultraviolet absorber.

Layer 3.a green-sensitive gelatino silver chlorobromide emulsion of which approximately 80 mole percent of the halide is chloride and a pyrazolone magenta coupler of the type described in US. Pat. 2,600,788.

Layer 2.-a gelatin layer.

Layer l.applied directly upon paper support a bluesensitive gelatino silver chlorobromide emulsion of which approximately 98 mole percent of the halide is bromide and an acyl acetanilide yellow coupler of the type described in U.S. Pat. 2,875,057.

Samples A and B were prepared. A was composed of the layers as outlined, in each of the layers of which 0.54% of mucochloric acid (based on the weight of the gelatin) was used as the hardener. In Sample B each of the six layers contained 0.5%, based on the weight of the gelatin, of bis[tri(1-aziridinyl)phosphazo] sulfone. The various color photographic print samples were exposed and processed. It was found that the re flectance of Sample B represented a distinct improvement over that of Sample A at various wave lengths thus showing better stain properties.

Instead of the hardener employed any of the other hardeners referred to herein are useful in this connection showing less stain than like products having an aldehyde-type hardener therein.

As shown hereinafter, the aziridine hardener compounds in accordance with our invention harden carboxylated polymers.

EXAMPLE 5 Solutions in water were prepared, containing 5% by weight of the vehicle, 0.05% by weight of Triton X-200E surfactant (sodium salt of alkylaryl polyether sulfonate made by the Rohm and Haas Company and believed to have the formula:

CH3 NaOaSCH2CH2OCH2CH20 and 0.15% by weight of hardener (i.e., 3% of the weight of the vehicle) and coated on glass plates with a 12 mil coating knife. The coatings were kept for seven days at a temperature of 73.5-76 F. and a relative humidity of 3655%. Separate Samples of the resulting films were then removed from the plates and immersed in (1) distilled water at 23 C. and (2) dilute sodium hydroxide two solutions was started under nitrogen and with vigorous stirring:

(a) 100 g. of ethyl acrylate, g. of acrylic acid (b) 3.9 ml. of Triton 770, 0.2 g. of sodium, bisulfite in 125 ml. of water The additions were completed in eleven minutes and followed by twenty minutes of vigorous stirring. Conversion to polymer was quantitative giving a polymer with an inherent viscosity in acetone of 0.86. Neutralization of the emulsion (diluted to ten percent solids with percent aqueous isopropyl alcohol) with concentrated ammonium hydroxide in the presence of 15 percent aqueous isopropyl alcohol produced a solution at pH solution (pH 10.2) at 23 C. with the following results: 15 6.8 with excellent clarity. Triton 770 is a surfactant sold TABLE III Properties of Film Vehicle Hardener Distilled water Water at pH 10.2

Item No l None Dissolves readily Dlssolves readily.

2 bis[tri(1-azi.ridiny1)phosphazo1su1fone Firm Firm- 0 3 CH3N=P(N 1) Swollen, soft Swollen, soft;

O 4 |SIN=P(N/) Swollen, firm Swollen, firm.

II a 0 5 Cl CCN=P -N Swollen, soft Partially disll a integrates. o

6 None Dissolves slowly Dissolves slowly.

H 0 0 /0H 7 N)P=N- N=P(N Firm Firm.

/ a ll 3 8 bis[trl(1-aziridinyl)phosphaz01sulione Firm Firm.

9 HardenerD of TableI Firm Firm.

The carboxylated vehicle employed in items 1-5 of by Rohm and Haas Company, and it is described as the Table III designated by is the sodium salt of the carsodium salt of an alkylaryl polyether sulfate. boxy-ester lactone of a vinyl acetate-maleic anhydride The carboxylated polymers which can be hardened with interpolymer. The preparation of the polymeric carboxythe hardening compounds of our invention are not reester lactone just mentioned is described in Example 2 of stricted to those specifically disclosed in Examples 5 and 6. U.S. Pat. 3,169,946. The conversion of the polymeric The carboxylated polymers (i.e., polymers containing carcarboxy-ester lactone to the sodium salt, as well as to boxyl groups) can be any of those shown in Yudelson other alkali metal salts such as the lithium salt, for U.S. Pat. 3,017,280, issued Jan. 16, 1962, in the form of example, is shown in Examples 17, 19, 20, 21, 22 and 23 their alkali metal salts. The various types of carboxyl conof Minsk U.S. Pat. 3,169,946, issued Feb. 16, 1965. The taining polymers are disclosed starting at line 37 of colother alkali metal salts, such as the lithium and poumn 1 and ending at line 8 of column 2. Examples 1-11 tassium salts, for example, of the carboxy-ester lactone of the Yudelson patent discloses the hardening of various of a copolymer prepared from maleic anhydride and vinyl carboxylated polymers in their ammonium salt form. acetfim can be p y d the Vehicle in Place of the These polymers in their alkali metal salt form, such as sodlum Salt form used In Items of Table In The their sodium salt form, can be hardened with the hardener sodium salt form is preferred, for example, for reasons 0 Compounds f our invention. of economy- The particular manner in which the carboxylated poly- T 1131c cargoxylated wehlge empl y i 1H S mers are prepared is not part of our invention. As shown 6 eslgnf'ted 15 g pupa? th by Yudelson U.S. Pat. 3,017,280, they can be prepared by e emu S1011 p0 ylnenza o .welg percen e y the solution or dope polymerization method using azo bis acrylate and 20 welght percent acryllc acid in the presence .sobut r0 a a Cat 31 St r b an 1 n I of potassium persulfate catalyst. Its preparation is del 5 s A h y i scribed in Example 6, hereinaften 12a ion ec mque. s s own 0 t ose s 1 e 1n t e po ymerization art, catalysts other than those specifically dis- EXAMPLE 6 closed herein can be employed in the polymerization A solution of 3.9 ml. of Triton 770 (40 percent mareactions. terial was used in this example) in 375 ml. of distilled Alkyl acrylates that can be employed in the polymerizawater was prepared under nitrogen and heated to 80 'tion reaction with acrylic acid include, for example, in a constant temperature bath. To this -was added 1.5 methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl g. of potassium persulfate and 0.3 g. of sodium bisulfite. acrylate, methyl methacrylate, ethyl methacrylate, n-pro- Immediately the simultaneous addition of the following pylacrylate and n-butyl methacrylate. Methacrylic acid can be substituted for acrylic acid in the polymerization reactions just noted.

The carboxylated polymers can be used as the vehicle in silver halide photographic emulsions, such as silver chloride and silver bromoiodide emulsions, for example. These emulsions can 'be hardened with one or more of the hardening compounds used in hardening the various hydrophilic colloids disclosed herein. Mixtures of gelatin and at least one of the other hydrophilic colloids can be used to form compositions containing no silver halide or to form silver halide emulsions and the resulting compositions can be hardened with one or more of the hardening compounds used by us.

The high speed silver bromoiodide emulsion referred to hereinbefore is of the type described by A.P.H. T rivelli and W. F. Smith in The Photographic Journal, vol. 79, pages 330-338 (1939).

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinbefore.

We claim:

1. A composition of matter comprising a hydrophilic colloid and a hardening amount of an aziridine hardener selected from the aziridine hardener compounds having the formulas:

1). (D ftal).

wherein X is CO, S CO(CH CO, SO (CH SO COC H CO, SO C H SO SO C H CO,

CO CH C, H (CH CO R is Cl C, phenyl,

a low carbon alkyl hydrocarbon radical or an aralkyl radical, Y is CO or S0 and n is a small whole number.

2. A composition of matter in accordance with claim 1 wherein the hydrophilic colloid is gelatin.

3. A composition of matter in accordance with claim 1 wherein the hydrophilic colloid is a carboxylated polymer.

4. A composition of matter in accordance with claim 1 wherein the hydrophilic colloid is an alkali metal salt of a carboxy-ester lactone of a copolymer prepared from maleic anhydride and vinyl acetate.

5. A composition of matter in accordance with claim 1 wherein the hydrophilic colloid is the sodium salt of a carboxy-ester lactone of a copolymer prepared from maleic anhydride and vinyl acetate.

6. A composition of matter in accordance with claim 1 wherein the hydrophilic colloid is a copolymer prepared from acrylic acid and ethyl acrylate.

7. A composition of matter comprising a hydrophilic colloid and a hardening amount of bis{tri(1-aziridinyl) phosphazo}sulfone.

8. A composition of matter in accordance with claim 7 wherein the hydrophilic colloid is gelatin.

9. A composition of matter in accordance with claim 7 wherein the hydrophilic colloid is a carboxylated polymer.

amount of Cl OCN=P a u i a 13. A composition of matter in accordance with claim 12 wherein the hydrophilic colloid is the sodium salt of a carboxy-ester lactone of a copolymer prepared from maleic anhydride and vinyl acetate.

14. A composition of matter in accordance with claim 1 comprising a hydrophilic colloid and a hardening amount of 15. A composition of matter in accordance with claim 14 wherein the hydrophilic colloid is a copolymer prepared from acrylic acid and ethyl acrylate.

16. A composition of matter in accordance with claim 1 comprising a hydrophilic colloid and a hardening amount of 17. A composition of matter in accordance with claim 16 wherein the hydrophilic colloid is a copolymer prepared from acrylic acid and ethyl acrylate.

18. A composition of matter in accordance with claim 1 wherein the hydrophilic colloid is the sodium salt of a carboXy-ester lactone of a copolymer prepared from maleic anhydride and vinyl acetate and the hardener is 19. A composition of matter in accordance with claim 1 wherein the hydrophilic colloid is the sodium salt of a carboxy-ester lactone of a copolymer prepared from maleic anhydride and vinyl acetate and the hardener is 20. A composition of matter in accordance with claim 1 wherein the hydrophilic colloid is the sodium salt of a carboXy-ester lactone of a copolymer prepared from maleic anhydride and vinyl acetate and the hardener is 21. A composition of matter in accordance with claim 1 wherein the hydrophilic colloid is gelatin and the hardener is 22. A composition of matter in accordance with claim 1 wherein the hydrophilic colloid is gelatin and the hardener is ener is 24. A composition of matter in accordance with claim 1 wherein the hydrophilic colloid is gelatin and the hard- P'COH4[ C O-N=P (N ener is 25. A composition of matter in accordance with claim 1 wherein the hydrophilic colloid is gelatin and the hardener is 26. A composition of matter in accordance with claim 1 wherein the hydrophilic colloid is gelatin and the hardener is 27. A gelatin-silver halide photographic emulsion containing a hardening amount of an aziridine compound 12' selected from the aziridine hardener compounds having the formulas set forth in claim 1.

28. A gelatin-silver halide photographic emulsion containing a color coupler and a hardening amount of an aziridine compound selected from the aziridine hardener compounds having the formulas set forth in claim 1.

29. A gelatin-silver halide photographic emulsion in accordance with claim 27 containing as the hardener therein a hardening amount of bis{tri(l-aziridinyDphosphazo}sulfone.

30. A gelatin-silver halide photographic emulsion in accordance with claim 28 containing a color coupler and a hardening amount of bis{tri(1-aziridinyl)ph0sphazo}- sulfone.

References Cited UNITED STATES PATENTS 2,964,404 12/1960 Burness 96-85 FOREIGN PATENTS 1,224,860 6/1960 France 96111 NORMAN G. TORCHIN, Primary Examiner R. E. FIGHTER, Assistant Examiner U.S. Cl. X.R. 

